Organic phosphorus-containing lubricants



i ful lubricant compositions.

- invention to provide internal combustion engine, bearing,

United States Patent 3,243,370 ORGANIC PHOSPHORUS-CONTAINING LUBRICANTS Gail H. Birum, Kirkwood, Mo., assignor to Monsanto Company, a corporation of Delaware No Drawing. Filed Nov. 6, 1961, Ser. No. 150,158 22 Claims. (Cl. 25246.6)

This application is a continuation-impart of the following copending applications: Serial No. 27,505, filed May 9, 1960, now U.S. Patent 3,014,944, which is a continuation-in-part of application Serial No. 780,209, filed December 15, 195 8, now abandoned; Serial No. 780,224, filed December 15, 1958, now U.S. Patent 3,014,950; Serial No. 780,262, filed December 15, 1958, now U.S. Patent 3,014,951; Serial No. 820,618, filed June 1 6, 1959, now U.S. Patent 3,014,954; Serial No. 828,464, filed July 21, 1959, now U.S. Patent 3,014,956; Serial No. 841,443, filed September 22, 1959, now U.S. Patent 3,042,698; Serial No. 841,450, filed September 22, 1959, now U.S. Patent 3,020,306; Serial No. 844,206, filed October 5, 1959, now U.S. Patent 3,042,699; Serial No. 846,817, filed October 21, 1959, now U.S. Patent 3,042,700; Serial No. 847,684, filed October 21, 1959, now U.S. Patent 3,042,701; Serial No. 852,206, filed November 12, 1959, now U.S. Patent 3,042,702; Serial No. 40,531, filed July 5, 1960, now U.S. Patent 3,014,945, which is a continuation-in-part of application Serial No. 780,202, filed December 15, 1958, now abandoned; Serial No. 40,550, filed July 5, 1960, now U.S. Patent 3,014,946, which is a continuation-in-part of application Serial No. 780,222, filed December 15, 1958, now abandoned; Serial No. 40,551, filed July 5, 1960, now U.S. Patent 3,014,947, which is a continuation-in-part of application Serial No. 780,223, filed December 15, 1958, now abandoned; and Serial No. 74,228, filed December 7, 1960, now U.S. Patent 3,014,948, which is a continuation-in-part of application Serial No. 780,221, filed December 15, 1958, now abandoned.

This invention relates to lubricant compositions. More particularly, this invention relates to lubricant compositions having improved extreme pressure, anti-wear, and anti-oxidant properties.

It is an object of this invention to provide new and use- It is a further object of this and gear oil lubricant compositions having improvedextreme pressure, anti-wear, and anti-oxidant properties. Other objects, aspects, and advantages of the invention will appear as the description proceeds.

It has been found according to this invention that mineral oil lubricant stocks can be improved by incorporating into the lubricant oil composition a minor amount by weight, based on the lubricant oil composition, sutficient to inhibit oxidation, inhibit wear, and to impart extreme pressure lubricating qualities to the composition of a compound which has the formula 1 limit.

where n is a number of 0 to 2, m is a number of 0 to 100 where n is 2 and 0 when n is less than 2, Y is selected from the class consisting of =P, EP:O, and zP qS, each R is selected from the class consisting of hydrocarbyl, halohydrocarbyl, hydrocarbyloxy, halohydrocarbyloxy, hydrocarbylthio and halohydrocarbylthio radicals which are free of aliphatic unsaturation and contain from 1 to 12 carbon atoms and wherein two R radicals taken together stand-for a radical selected from the class consisting of O-hydrocarbylene-O and --O-halohydrocarbylene-O radicals which are free of aliphatic unsaturation and which contain from 2 to carbon atoms;

R is selected from the class consisting of hydrocarbyl, halohydrocarbyl, hydrocarbyloxy, halohydrocarbyloxy, hydrocarbylthio and halohydrocarbylthio radicals which are free of aliphatic unsaturation and contain from 1 to 12 carbon atoms; Z is selected from the class consisting of hydrogen and hydrocarbyl radicals which are free of aliphatic unsaturation and which contain from 1 to -17 carbon atoms when n is 2 and from 1 to 10 carbon atoms when n is less than 2; Z is selected from the class con sisting of hydrogen and the methyl radical and is methyl only when Z is an alkyl radical of from 1 to 2 carbon atoms; and, when n is 2, Z and Z taken together with the carbon atom to which they are attached complete the cyclohexane ring; and R' and R" are selected from the class consisting of alkyl, haloalkyl, aryl, haloaryl, alkoxy, and haloalkoxy radicals of from 1 to 12 carbon atoms. By a hydrocarbyl radical is meant a radical obtained by removing a hydrogen atom from a hydrocarbon. Generically, by a hydrocarbylene radical is meant a radical obtained by removing two hydrogen atoms from different carbon atoms of the hydrocarbon. A hydrocarbylidene radical is one derived by removing two hydrogen atoms from the same carbon atom of the hydrocarbon. Such radicals are included within the above defmition.

Examples of preferred types of compounds within the above given definition are:

(A) 1 [bis(haloalkoxy)phosphinyl]alkyl bis(haloalkyl) phosphites, phosphates and phosphorothioates which are particularly useful as extreme pressure, anti-wear, and anti-oxidant lubricant additives, specific examples of this type of compound being 1-[-bis(2-chloropropoxy) phosphiny-lJethyl bis(2-chloropropyl) phosphite, 1-[bis(2- chloropropoxy) phosphinyl] heptyl (2-chloropropyl phosphate, and 1 [bis(2 chlorophopoxy)phosphinyl]heptyl bis(2-chloropropy1) phosphorothjoate;

(B) 2 [l-(dialkoxyphosphinyl)hydrocarbyloxy]-1,3,2- dioxaphospholanes of the formula 0 O II A POCHP(OT)1 wherein A is a hydrocarbylene radical which is free of aliphatic unsaturation and contains from 2 to 10 carbon atoms, Z denotes a hydrocarbyl radical which is free of aliphatic unsaturation and contains from 1 to 17 car bon atoms, including cycloalkylene radicals, and T denotes an alkyl radical of from 1 to 12 car-hon atoms. Examples of such compounds are 2-[l-(dihexyloxyphosphinyl)cyclohexyloxy] 1,3,2 dioxa 4,5-benzophospholane and 2 [Z-(diethoxyphosphinyl)propyl]-1,3,2-dioxaphospholane, which compounds impart good anti-wear, extreme pressure, and anti-oxidant properties to lubricant compositions.

(C) 1 (dia-lkoxyphosphinyl)alkyl bis[S (haloaryl)] phosphorodithioites. An example of this type of compound is l-(diethoxyphosphinyl)propyl S,S-bis(p-chlorophenyl) phosphorodithioite.

The amount of the phosphinylhydrocarbyloxy phos phorus ester of the above defined type which is used to provide the improved lubricant oil compositions of this invention will vary depending upon the lubricant oil vehicle to which it is added. Generally, the phosphonylhydrocarbyloxy phosphorus ester can be used in minor amounts based on the mineral oil lubricant base stock varying from 0.01% to 20% by weight. Preferably, amounts of the phosphorus ester ranging from 0.1% to 10% by weight are used. For example, for use in heavy duty hypoid gear oil compositions of approximately 120 SAE weight amounts of the phosphinylhydrocarbyloxy phosphorus ester on the order of about 1% to about 5% by weight of the lubricant base oil can be used to impart good extreme pressure and anti-wear properties to the lubricant gear oil composition. Internal combustion engine lubricant oil compositions of this invention may contain from 0.01% to 5% by weight of the phosphinylhydrocarbyloxy phosphorus ester based on the SAE -30 weight mineral lubricating oil, with amounts onthe order of about 0.1% to about 2% by Weight being preferred.

Many of the presently useful phosphorus compounds may be prepared by the reaction of a trivalent phosphorus compound having a halogen atom linked to the phosphorus atom thereof, a carbonyl compound, and an ester of a trivalent phosphorus acid, substantially as described in my copending application Serial No. 27,505, filed May 9, 1960, now US. Patent 3,014,944, which application is a continuation-impart of my application Serial No. 780,209, filed Dec. 15, 1958, now abandoned, of which two applications this application is a continuation-in-part. This reaction proceedsas fol-lows:

where R, R and R", Z, Z and n are as herein defined, X is selected from the class consisting of chlorine and bromine, and T is selected from the class consisting of a-lkyl and haloalkyl radicals of from 1 to 12 carbon atoms.

The above reaction takes place by using substantially the number of moles of the aldehyde or ketone, ZCZO, and the trivalent phosphorus ester RR"POT which is substantially equal to the number of halogen atoms present in the phosphorus-halogen compound R PX Thus, if the phosphorus-halogen compound is phosphorus trichloride, the product has the formula When the phosphorus-halogen compound is, say, a dihalide such as phenyl phosphorodich'loridite, the product has the formula When the phosphorus halogen compound is a mono-halide such as 2-chloro-l,3,2-dioxaphospl1olane, the product has the formula CHz-O The trivalent phosphorus atom of those compounds which are derived from a bis(haloalky'l) phosphorohali- (lite or from a haloalkyl phosphonohalidite, an aldehyde and a trivalent phosphorus ester in substantially equimolar amounts can be converted to the pentavalent state by heat rearrangement. For example, bis(2-chloroethyl) phosp'horochloridite, acetaldehyde, and triethyl phosphite react together to give the bis(Z-chloroethyl) phosphite of diethyl 1-hydroxyethylphosphonate which, upon heating, is rearranged as follows:

(01011201120)PooHi woHzOHm o1oH2oHzi 0oHiiwoHzoHm ClCHzOHzO CH3 Heat isomerization of the products obtained from a haloalkyl phosphonohalidite, an aldehyde, and a trivalent phosphorus ester proceeds, e.g., as follows:

My application Serial No. 828,464, filed July 21, 1959, now US. Patent 3,014,956, of which this application is a continuation-in-part, describes preparation of the pentavalent phosphorus compounds by heat isomerization of the haloalkyl trivalent phosphorus esters which takes place substantially according to the scheme:

where X is chlorine or bromine and R, R, R", Z and Z are as defined above.

It will thus be evident that numerous compounds having one trivalent phosphorus atom and from one to three pentavalent phosphorus atoms are obtained by reacting together a trivalent phosphorus-halogen compound with the number of moles of an aldehyde and a trivalent phosphorus ester which are equal to the number of halogen atoms present in the phosphorus-halogen reactant; that numerous compounds having phosphorus present only in the pentavalent state are obtained by subsequent reaction with oxygen or sulfur whereby addition of the oxygen or sulfur takes place at the trivalent phosphorus atom; and that many compounds having phosphorus present only in the pentavalent form are obtained by heat rearrangement of a haloalkyl trivalent phosphorus ester of an a-hydroxyphosphonate. All of such products can be defined by the general formula:

where R, R, R", Z, Z, Y and n are as defined above, and they are all prepared by initially starting with a quantity of the aldehyde and a quantity of the trivalent phosphorus ester which are substantially equal to the number of halogen atoms present in the phosphorus-halogen compound. The treatment with oxygen or sulfur or the heat treatment are subsequent steps which aiTect only a portion of the initial molecule, i.e., that which is derived from the phosphorus-halogen compound. Such subsequent treatment provides compounds having improved thermal stability and very good resistance to hydrolysis by water. Hence, for some purposes, those of the compounds which contain phosphorus only in the pentavalent form are particularly useful adjuvants for lubricant compositions,

Some of the initial products, i.e., those containing one trivalent phosphorus atom present as a part of an alkyl or haloalkyl phosphite or phosphonite structure, can be converted to still other compounds of present utility. Such initial products, esters of a trivalent phosphorus acid, can react with additional quantities of a mono-halogen phosphorus compound and of an aldehyde or ketone; thus when T is an alkyl or halo-alkyl radical and R, R, and R are as herein defined the following occurs:

Of course, if in the phosphorus halogen compound at least one of the Rs is an alkoxy or haloalkoxy radical, the compound (II) would have the structure Here again, in (III), there is the alkyl or haloalkyl trivalent phosphorus ester structure required for reaction with a phosphorus halogen compound and an aldehyde; (III) thus reacts as follows:

The compound (IV) obviously has the formula where n is 2. Compound (III) has the same structure, with n being 1; and in the initial product, i.e., (I), n is zero. Of course, the further reaction of (IV) will depend upon whether the trivalent phosphorus atom is attached .to at least one alkoxy or haloalkoxy radical, since such a radical is required for reaction with a further quantity of phosphorus halogen compound and aldehyde. Bear ing this in mind, compounds of the structure (V) wherein n has an increasingly greater value are obtained by prolonged addition of phosphorus halogen compound and aldehyde to intermediately formed products. Reaction ceases when the required quantities of carbonyl compound and halogen compound are no longer available or whenever there is formed as product a compound which does not possess the required phosphite (TO) PO or phosphonite TOP (R) O structure.

A very convenient method of preparing compounds having the structure (V), where n is at least 1, is de- 6 scribed in my copending application Serial No. 820,618, filed June 16, 1959, now U.S. Patent 3,014,954, of which the present application is a continuation-in-part. According to this method, the ratio of trivalent phosphorus ester, carbonyl compound and trivalent phosphorus halogen compound which are reacted together is such that the carbonyl compound and halogen compound are present in substantially equimolar proportions and the trivalent phosphorus ester is present in less than an equimolar proportion with respect to the other two reactants. With such a ratio, using as the phosphorus halogen compound an ester of either phosphorochloridic acid or an ester of phosphonochloridic acid, there is first formed the 1:1:1 product:

Z 0 TOPO( )i R t z B where T is an alkyl or haloalkyl radical of 1 to 12 carbon atoms. Formation of the 1:1:1 product uses up the originally present trivalent phosphorus ester; and the excess of aldehyde and phosphorus halogen compound reacts with the newly formed trivalent phosphorus ester, i.e., the 1:1:1 product, to give products of the formula t Ft il l TOPOO----POC----PR L| I R Z R Z n R where n is at least 1. The value of n is a function of the quantity of phosphorus halogen compound and of the carbonyl compound which is available for reaction of intermediately formed products.

A commercially attractive process for preparing mixtures consisting of a phosphorus-halogen compound and a trivalent phosphorus ester, which mixtures can then be reacted with a carbonyl compound to give the presently useful products, comprises reaction of an oxirane compound with phosphorus trichloride or phosphorus tribromide in certain proportions as disclosed in my copending application, Serial No. 780,262, filed December 15, 1958, now U.S. Patent 3,014,951, of which the present application is a continuation-iu-part. The reaction of 5 moles of an oxirane compound, e.g., an alkylene oxide, with 2 moles of a phosphorus halide results in the production of essentially an equimolar mixture of phosphorohalidite and phosphite; e.g., with ethylene oxide as the oxirane compound and phosphorus trichloride there is obtained an essentially equimolar mixture of bis(2-chloroethyl) phosphorochloridite and tris(2-chloroethyl) phosphite. This mixture is then reacted with an aldehyde or ketone to give the phosphite-phosphonate. However, when 2 moles of the phosphorus halide is reacted with less than 5 but more than 4 moles of the oxirane compound, the phosphorohalidite and the phosphite are not formed in equimolar proportion; instead, the phosphorohalidite is in excess. Thus, with 4.8 moles of ethylene oxide and 2 moles of phosphorus trichloride there are obtained 1.5 moles of bis(2-chloroethyl) phosphorochloridite, and with only 4.09 moles of the oxide per mole of the trichloride there are obtained 21 moles of the phosphorochloridite per mole of the phosphite. As disclosed in my copending application Serial No. 820,618, filed June 16, 1959, now U.S. Patent 3,014,954, mixtures of phosphorohalidite and phosphite prepared by reaction of 2 moles of phosphorus trichloride or tribromide with less than 5 moles but more than 4 moles of an oxirane compound are particularly useful for preparing those of the presently useful compounds which have a plurality of the units Here, the excess of phosphorohalidite with respect to phosphite which is required to produce compounds of this type is conveniently present. Thus, when the ratio of phosphorohalidite to phosphite is 21:1, the addition of aldehyde in a quantity which is equimolar with respect to the halidite results in the production of a product having an average of 20 such units, e.g., from ethylene oxide, phosphorus trichloride and propionaldehyde, the following product is obtained:

where n has an average value of 20. Because the reaction of each intermediately formed product with the excess of phosphorochloridite and aldehyde proceeds very rapidly, the product obtained is a mixture having varying values for n. Hence, the value given above, ascertained by the quantity of reactants consumed and by elemental analysis, is necessarily an average value. Actually, the product probably consists of mixtures in which n will vary from, say, to as high as 50, with the average being 20. Those compounds wherein the value of n, i.e., the number of repeating units,

is an average value between 0 and 1, or between two successive whole numbers, such as in the cases wherein the value of n is 0.5, 1.3, 2.8, etc. are also intended to be within the scope of this invention since a product having such an intermediate value is really a mixture of products having lower and higher whole number values of n, which values depend upon the molar ratio of the reactants used to prepare the starting materials.

Compounds containing a plurality of the units can be isomerized as disclosed in my copending application Serial No. 828,464, filed July 21, 1959, now US. Patent 3,014,956, or oxidized or thionated to give products having phosphorus present only in the pentavalent form, as disclosed in my copending application Serial No. 847,684, filed October 21, 1959, now US. Patent 3,042,701, of which the present application is a continuation-in-part. Thus, upon reaction with oxygen or sulfur the trivalent phosphorus atom is rendered pentavalent and the products have the formula wherein E is oxygen or sulfur.

The more simple of the present compounds, i.e., those prepared from an equimolar mixture of a diester of phosphorochloridous acid, an aldehyde, and a tribasic phosphite, can be named as phosphites of l-hydroxyalkylphosphonates. Thus the 1:121 reaction product of bis(2- .chloroethyl) phosphorochloridite, butyraldehyde and tris- (2-chloroethyl) phosphite, said reaction product having the structure it is believed that understanding of the invention will be best facilitated by simply presenting the structural formula of each compound as reference to it is necessary.

In the simple 1:1:1 reaction product that portion which is derived from the mono-halo phosphorus compound is That portion which is derived from the aldehyde or ketone is Z! O C and that portion which is derived from the tribasic trivalent phosphorus ester is 0 ll PR Hence, it will be readily evident that a compound of the formula CH2--O\ (H) POCHP(OCH )2 CHz-O phenyl of an aldehyde or ketone and less than one mole of the t-ri-basic trivalent phosphorus ester,

I ll Lt 11'.

the portion is derived from the mono-halo phosphorus compound,

is derived from the aldehyde or ketone, the portion 9 is derived from the same mono-halo phosphorus compound and the same aldehyde or ketone and the portion is derived from the tribasic phosphorus ester. Hence, the

product I"? l i (CH CH2O)2POCH2P--OCH2- -P(OCH3)2 J LOCHzCH; u

Here, the portion RP= is derived from the phosphorus dihalide, RPX where X is chlorine and bromine and, as in the instances above, the portions are derived from the aldehyde or ketone and the tribasic trivalent phosphite, respectively.

The product obtained from 1 mole of a phosphorushal-ogen compound containing 3 replaceable halogen atoms and 3 moles each of the aldehyde or ketone and of the tribasic trivalent phosphorus ester has the formula F t 1=--o C-PR L t a Here, the compound was obviously derived from PX where X is chlorine or bromine, i.e., phosphorus trichloride or phosphorus tribromide or a mixed phosphorus trihalide having both chlorine and bromine. The portions are derived from the aldehyde or ketone and tribasic trivalent phosphorus ester.

As disclosed above, the trivalent phosphorus atom of the above reaction products is readily converted to the pentavalent form by oxidation or thionation. Hence, compounds of the formula are derived by oxidation or thionation of the compounds moti e RZR and compounds of the formula where n is at least 1 are derived by oxidation or thionation of the compounds 0 F H I ll i? ii*i R z LR Z l., R

As disclosed above, compounds in which all of the phosphorus is pentavalent are also obtained by heat rearrangement of a product in which at least one R of the portion is a haloalkoxy radical, Hence the compounds where n is a number of 0 to are obtained either by the oxidation of z 0 Z 0 l n 1| haloa1ky1-1FO(l3---1FOCPR" B LR LL l or by the heat rearrangement of O O l [I] I1 ll ha1oa1ky1-01l 0(|3----I|'oo -lrrt" R Z R Z L R Those of the products which have been obtained by replacement of 2 or 3 halogen atoms of the phosphorus halogen compound, i.e., products of the formula It L 2 also undergo oxidation or thionation. Hence the compound of the formula is obviously obtained by thionation of the reaction product of 1 mole of phenylphosphonous dichloride or dibromide with 2 moles each of acetaldehyde and trimethyl phosphite. And the compound of the formula phenyl is obviously obtained by oxidation of the product obtained by reacting 1 mole of phosphorus tn'chloride or tribromide with 3 moles each of benzaldehyde and tris(2- chloropropyl) phosphite.

In the working examples of the invention which are provided herein, for the sake of brevity in some cases, the reactants from which the lubricant additives are prepared are not shown, in view of the ease with which the starting materials can be ascertained by inspection of the structural formula as summarized above. The method of preparing the presently useful additives, broadly, are briefly as follows:

The three reactants, i.e., the phosphorus halogen compound, the aldehyde and the tribasic trivalent phosphorus ester are mixed together in the proportions referred to above, either at ordinary, decreased or increased temperatures. Because, generally, an exothermic reaction occurs, it is usually advisable .to contact the reactants with each other in the cold and then to apply heat only if no reaction is evidenced after all three reactants are mixed. After reaction has ceased, which can be noted by lack of change in temperature or in viscosity, the by-product halide and possibly any unreacted original material is removed, e.g., by distillation or extraction. Depending upon the proportion of reactants employed, the residue is the substantially pure product of the structure I I I ll l ll RnPOC----POC--1"R" l l Liv t1... R Where n is a number of to 2, m is a number of 0 to 100 when n is 2 and 0 when n is less than 2, and R, Z, Z, R, R" and R' are hereinbefore defined. All of such compounds can be oxidized by treatment with an oxidizing agent such as oxygen, ozone, hydrogen peroxide, a hydroperoxide, a nitrogen oxide, or a percarboxylic acid atordinary or decreased temperatures; and all of such compounds can be thionated by treatment with sulfur at either ordinary temperatures or at temperatures which may be up to 180 C. The products thus obtained have the formula E 2 II I I where E is oxygen or sulfur.

Also, those of the trivalent phosphorus compounds in which at least one R is a haloalkoxy radical, can be rearranged by heating at a temperature of 135-225 C. to give the compounds n. haloalkyl-ll o (:3 1 0 (ll-----ll R" R Z R"'z R The trivalent phosphorus halogen component which is generally useful for reaction with an aldehyde and a tribasic, trivalent phosphorus ester has the formula O-halohydrocarbylene-O radicals which are free of aliphatic unsaturation and contain from 2 to carbon atoms. This includes compounds of the following structures, where A denotes a hydrocarbyl radical of from 1 to 12 carbon atoms or said hydrocarbyl radical containing halogen substituent and X is chlorine or bromine PX (AS) PX APX (AO) (AS)PX AOPX A PX Particularly useful also are the dioxy compounds of the formula wherein A is selected from the class consisting of hydrocarbylene radicals of 2 to 10 carbon atoms and halogensubstitution products thereof.

Examples of trivalent phophorus halogen compounds having the above formulas and useful for the present purpose are, of course, phosphorus trichoride, phosphorus tribromide and mixed phosphorus bromide chlorides insofar as PX is concerned.

Compounds of the formula AOPX are hydrocarbyl or halohydrocarbyl phosphorodichloridites or dibromidites. The hydroc'aubyl radicals may be alkyl, cycloalkyl, aryl, alkaryl or aralkyl and such hydrocarbyl radicals may be substituted with one or more atoms of halogen. Examples of the presently usef-ul aliphatic phosphorodih-alidites are methyl, ethyl, n-propyl, isopropyl, allyl, nbutyl, isobutyl, tert-butyl, amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, Z-ethylhexyl, isononyl, n-decyl, n-undecyl, n-dodecyl, 2-chloroe'thyl, 2-fiuoroethyl, tetrachlorob-utyl, Z-chloropropyl, S-chloropentyl, tribrornopropyl, 2- iodopropyl, 3-bromo-2-chloropropyl, dichlorododecyl or octachlorohexyl phosphorodichloridite or phosphorodibromidite. Examples of the presently useful cyoloal'kyl or halocycloalkyl phosph-orodihalidites are cyclohexyl, cycl'opentyl, cyclopropy-l, Z-methylcyclopentyl, 4-isopropylcyclohexyl, 2,4-dichlorocyclopentyl, 2-bromo-2-methy1- cyclohexyl, 2-fluorocyclopentyl, 2-hexylcyclohexyl, or tetrachlorocyclohexyl phosphorodichloridite or phosphorodi bromidite. Examples of the benzenoid phosphorod i'halidite's are phenyl, 04- or fi-naphthyl, 4 b'iphenylyl, 0-, mor p-tolyl, 2,4-dichlorophenyl, p-ethylphenyl, dibutylphenyl, mesityl, curnyl, o-, rnor p-pentylphenyl, Z-butylphenyl, benzyl, 2-phenylethyl, 4-isopropylbenzyl, 2-ethyl-4-chlorobenzyl, or u-naphthylmethylphcsphorodichloridite.

Compounds of the formula ASPX are phosphorodihalidothioites. Such compounds are, e.g., the alkyl esters such as ethyl, n butyl, Z-ethylhexyl, octyl or dodecyl phosphorodichloridothioite or phosphorodi-bromidothioite; the cycloalkyl esters such as cyclohexyl, 2-methylcyclopentyl or 2,4-dimethylcyclohexyl pho-sphorodichloridothioite of phosphorodibromidothioite; and the halogen substituted esters such as 2-chloroethyl, 3-iodopropyl, 3,3- dibromopropyl, 2-fluo-ro'ethy-l, iodooctyl, bromododecyl, tetrafluorocyclopentyl, 2-chlorocyclohexyl or tribromocyclopentyl phospho-rodichloridothioite or phosphorodibromidothioite. Examples of the presently useful benzenoid phosphorodihalidothioites are phenyl phosphorodichloridothioite, fl-ethyl-a-naphthyl phosphorodichloridothioite, benzyl pho'sphorodichloridothioite, 4 biphenyly-1 phosphoro'dichloridothioite, etc.

The benzenoid phosphorodichloridites or phosphorodichlor-idothioites may contain one or more halogen substituents in either the aromatic ring thereof, at an aliphatic group which is attached to the aromatic ring, or at both the aromatic ring and said aliphatic group. Ex-

amples of such halogen-substituted compounds are 2-,

3- or 4-chloropheny-l phosphorodichlorid ite or phosphorodichloridothioite; 3,4,5- or 2,3,4-trichlorophenyl phosphorodichloridite or phosphoro'dichlorid-othioite; 4-iodopheny-l ph-osphorodi'chloridite or phospho-rodichloridothioite; ,B-bromo-a-naphthyl phosphorodichlor-idite or phosphorodichl-oridothioite; 4-(trifiuoromethyl)phenyl phosphorodichloridite or phosphorodichloridothioiteg 2-chloroabromobenzyl phosphorodichloridite or phosphorodichloridothioite; 4-(iod ophenyl)phenyl phosphorodiohlomd1te or phosphorodichloridothioite; octachlonolniphenylyl phosphorodichloridite or phosphorodichloridothioite, etc.

Presently useful compounds of the formula (AO) PX are dihydrooarbyl or bis(halo-hydrocanbyl) phosphorochlor-idites or phosphonoibromidites. Such compounds are, e.g., the alkyl esters such as dimethyl, diethyl, dipropyl, diisopropyl, diisobutyl, rdi-n-butyl, di-tert-butyl, di-n-pentyl, diis-opentyl, di-n-h-exyl, di-n-heptyl, bis(2- ethylhexyl), di-n-octyl, d'iisononyl, di-n-decy'l, di-n-undecyl, di-n-dodecy-l or di-tert-dodecyl phosphorochloridite, or phosphorobromidite or the mixed esters such as ethyl 13 methyl phosphorochloridite, ethyl propyl phosphorochloridite, n-octyl n-tpropyl phosphorobromidite, tertairnyl n-dodecyl phosphorochloridite, etc.

The alkyl radical of the phosphorochloridite or phosphorobromidite may be substituted by one or more halogen atoms. Examples of presently useful bishhaloalkyl) compounds are the simple esters such as bis(2-ohloroethyl), bis(3-bromopropyl), bis(3-chloroflautyl), bis(dichlorooctyl), bis(2 fluoroethyl), bis(hexachlorododecyl) or bis(Z bnomo-Z-chloroethyl) phosphorochloridite or phosphorobromidite; the mixed esters such as Z-chloroethyl 3-bromopropyl phosphorochloridite or Z-fluoroethyl tetrachlorobutyl phosphorobromidite; and mixed esters of both hydrocarbyl and halohydrocar'byl alcohols such as 2-chloroethyl peutyl phosphorochloridite or 2- chloropropyl ethyl phosphorobromidite.

The corresponding aliphatic dihydrocarbyl phosphorohalidothioites which are useful for reaction with an aldehyde and a triorgano phosphite to give the presently employed lubricant additives are, e.g., dimethyl, diethyl, dipentyl, di-n-butyl, bis(2-ethylhexyl), didodecyl, ethyl methyl, butyl n-octyl or isopropyl methyl phosphorochloridothioite or phosphorobromidothioite. Examples of useful simple or mixed aliphatic halohydrocarbyl esters are bis(2-chloroethyl), bis(tetrabromobutyl), bis(3- fluoropropyl) or propyl trichlorododecyl phosphorochloridothioite or phosphorobromidothioite.

Also presently useful are the cycloaliphatic esters such as dicyclohexyl, dicyclopentyl, 2,3-dimethycyclohexenyl n-propyl, or bis(4-chlorocyclohexyl) phosphorochloridite or phosphorochloridothioite.

A class of aromatic trivalent phosphorus halides which are particularly suited for the present purpose are the benzenoid dihydrocarbyl phosphorohalidites, i.e., compounds of the formula in which Ar is a benzenoid hydrocarbyl radical of from 6 to 12 carbon atoms and X is chlorine or bromine. Such compounds may be diaryl, bis(alkaryl), bis(aralkyl), aryl alkaryl, aryl aralkyl, or alkaryl aralkyl phosphorochloridites, e.g., diphenyl, di-p-tolyl, di-aor fl-naphthyl, dibiphenylyl, dimesityl, dicumyl, bis(2-butylphenyl), phenyl a-naphthyl, biphenylyl phenyl, 4-ethylphenyl phenyl, dibenzyl, bis(2-ethylphenyl), benzyl phenyl, biphenylyl 4- ethylbenzyl, 3-phenylpropyl mesityl, or B-naphthylmethyl phenyl phosphorochloridite or phosphorobromidite. Mixed aliphatic aromatic esters such as ethyl phenyl phosphorochloridite or amyl biphenyl phosphorobromidite are also useful.

The corresponding benzenoid dihydrocarbyl phosphorohalidodithioites, i.e., compounds of the formula wherein Ar is as defined above, are similarly valuable for the present purpose. Such compounds are, for example, diphenyl phosphorochloridodithioite, dibenzyl phosphorobromidodithioite, di-,8-naphthyl phosphorochloridodithioite, biphenylyl phenyl phosphorochloridodithioite, benzyl a-naphthylmethyl phosphorobromidodithioite, p-tolyl 2- phenylethyl phosphorochloridodithioite, etc.

An example of a mixed aliphatic-aromatic ester of present utility is n-butyl phenyl phosphorochloridothioite. Other examples of mixed esters which may be used are methyl phenyl phosphorochloridite, Z-chloroethyl a-naphthyl phosphorochloridodithioite, benzyl butyl phosphorobromidite, n-butyl cyclohexyl phosphorochloridite, 2- ethylhexyl 2,3-dichlorophenyl phosphorochloridite, etc.

Presently useful trivalent phosphorus halides also in- 14 clude the O-hydrocarbyl S-hydrocarbyl phosphorochloridothioites, i.e., compounds of the formula AS--ILX wherein A and X are as above described. Such compounds are, for example, O,S-diphenyl; O-pentyl S-phenyl; O,S-di-fi-naphthyl; O,S-diethyl; O,S-di-m-tolyl; O-4-chlorophenyl S-biphenylyl; 0,,8-naphthylmethy1 S-phenyl; or O-n-butyl S-p-cumyl phosphorochloridothioites or phosphorobromidothioites.

Another class of the presently useful halides includes the dihydrocarbylphosphinous halides, i.e., compounds of the formula A PX wherein A and X are as above defined. Such compounds are, e.g., diethylphosphinous bromide, dibutylphosphinous chloride, diphenylphosphinous chloride, didecylphosphinous bromide, di-p-tolylphosphinous chloride, dicyclohexylphosphinous chloride, bis(2-ethylhexyl)phosphinous chloride, dibenzylphosphinous chloride, di-otor fl-naphthylphosphinous chloride, (Z-ethylphenyl)phenylphosphinous chloride, benzylbiphenylylphosphinous chloride, bis(4-pentylphenyl)phosphinous chloride, (dodecyl) phenylphosphinous bromide, etc.

Also useful in the reaction with aldehydes and triorgano phosphites are the hydrocarbyl hydrocarbylphosphonohalidites and phosphonohalidothioites, i.e., compounds of the formula AEi-X wherein A and X are as above defined and E denotes --O or fiS. Examples of such compounds are methyl, ethyl, pentyl, n-octyl, tert-dodecyl, 4-butylcyclohexyl, phenyl, p-tolyl, cyclohexylbenzyl, ot-naphthyl, or biphenylyl phenylphosphonochloridite or ethylphosphonochloridite; phenyl or 4-ethylphenyl benzylphosphonobromidite; n-butyl or ,B-naphthyl cyclopentylphosphonochloridite; cyclohexyl or benzyl biphenylylphosphonochloridothioite; phenyl or ethyl phenylphosphonochloridothioite, etc.

The above dihydrocarbyl phosphorochloridites, dihydrocarbylphosphorochloridodithioites, O hydrocarbyl S-hydrocarbyl phosphorochloridothioites, dihydrocarbylphosphinous chlorides, hydrocarbyl hydrocarbylphosphonochloridites and hydrocarbyl hydrocarbylphosphonochloridothioites may contain one or more halogen substituents in either an alkyl radical, a cycloalkyl radican, an aryl radical, at an aliphatic group which is attached to an aromatic or cycloaliphatic ring, or at both the aromatic or cycloaliphatic ring and at said aliphatic group. Examples of such halogen-substituted compounds are Bis( 2-, 3- or 4-chlorophenyl) phosphorochloridite or phosphorochloridodithioite Bis(2-, 3- or 4-bromophenyl) phosphorochloridite or phosphorochlorididithioite 0-2, 3- or 4-chloro or bromophenyl S-phenyl phosphorochloridothioite Bis(2,4-dichlorobenzyl) phosphorochloridite or phosphorobromidodithioite Bis (4-iodo-2-ethylphenyl) phosphorochloridite or phosphorochloridodithioite Bis[4- (fiuoroethyl)phenyl] phosphorochloridite or phosphorochloridodithioite Bis (pentachlorophenyl) phosphorochloridite or phosphorochloridodithioite Bis(a-chloro-,B-naphthyl) phosphorochloridite or phosphorochloridodithioite Bis(octachlorobiphenylyl) phosphorochloridite or phosphorochloridodithioite Bis(2-chloroethyl) phosphorochloridite or phosphorochloridodithioite esters have the formula Bis(2-chlor0propyl) phosphorochloridite or phosphorochloridodithioite Bis(3-fluoropropy1)phosphinous chloride Bis(2-chlorophenyl) phosphinous chloride 2-chloroethyl ethylphosphonochloridothioite Tetrachlorobutyl dodecylphosphonochloridite Methyl 4-chlorophenylphosphonochloridite 2-chloroethyl ethylphosphonochloridite Another class of trivalent phosphorus halides which are presently useful are the hydrocarbylphosphonous dihalides of the formula APX wherein A is a hydrocarbyl or halohydrocarbyl radical of from 1 to 12 carbon atoms and X is halogen or bromine. Examples of such dihalides are the aromatic phosphonous dihalides such as phenylphosphonous dichloride, 2-, 3- or 4-chlorophenylphosphonous dichloride, ocor fi-naphthylphosphonous dichloride, and 2-, 3- or 4-biphenylylphosphonous dichloride; the aliphatic phosphonous dichlorides such as methyl-, ethyl-, 2-chloroethyl-, isopropyl-, n-butyl-, tertbutyl-, trichlorobutyl-, n-pentyl-, n-hexyl-, 2-ethylhexyl-, n-octyl-, bromooctyl-, branched-chain nonly-, isodecyl-, n-dodecyl-, and tert-dodecylphosphonous dichloride; the aliphatic-aromatic phosphonous dichlorides such as mor p-tolylphosphonous dichloride, diisopropylphenyl phosphonous dichloride, mesitylphosphonous dichloride,

,n-hexylphenylphosphonous dichloride, [3-(2-chloroethyl)- m-napthylphosphonous dichloride, 4-chlorobenzylphosphonous dichloride, 0-, mor p-n-butylbenzylphosphonous dichloride, Z-phenylethylphosphonous dichloride and fl-naphthylmethylphosphonous dichloride; the cycloalkylphosphonons dichlorides such as cyclohexylphosphonous dichloride and cyclopentylphosphonous dichloride, etc.

Of pronounced utility in the presently provided process are cyclic esters of phosphorohalidous acid. Such wherein A is an alkylene or arylene radical having from 2 to 10 carbon atoms. Examples of compounds of the above formula are the various halo dioxaphospholanes, dioxaphosphorinanes, and dioxaphosphepanes, e.g., 2-chloroor 2-bromo-1,3,2-dioxaphospholane; 2chloro- 4 methyl 1,3,2 dioxaphospholane; 2 chloro 4,5- dirnethyl 1,3,2 dioxaphospholane; 2 bromo 1,3,2- dioxaphosphorinane; 2 chloro 4 methyl 1,3,2 dioxaphosphorinane; 2 chloro 1,3,2 dioxaphosphorinane; 2-chloro-1,3,2-dioxaphosphepane; 2-chloro-1,3,2- benzodioxaphosphole; 2 chloro 4,4,5,5 tetramethyldioxaphospholane; 2 chloro 4 chloromethyl 1,3,2- dioxaphospholane; 2,5 dichloro 1,3,2 dioxaphosphorinane; 2,6,7 trichloro 1,3,2 benzodioxaphosphole; 2,5 dibromo 1,3,2 dioxaphosphorinane; 2 chloro-- fluoro-l,3,2-dioxaphosphorinane, etc.

Any of the above described phosphorus-halogen compounds can be reacted with an aldehyde and a triorgano phosphite to give dior poly-phosphorus compounds which are useful per se as polymer adjuvants or which may be oxidized, sulfurized or heat-rearranged to give presently useful compounds.

The useful aldehydes have the formula ZCHO wherein Z is selected from the class consisting of hydrogen and hydrocarbyl radicals which are free of aliphatic unsaturation and which contain from 1 to 18 carbon atoms.

Owing to their easy availability, 21 particularly useful class of aldehydes includes the alkanecarboxaldehydes of from 1 to 18 carbon atoms, e.g., formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, hexanal, heptanal, 2-ethylhexanal, octanal, 2-butyloctanal, 6-methylheptanal, decanal, undecanal, Z-methylundecanal, lauraldehyde, stearaldehyde, tridecaldehyde, etc.

1 6 Presently useful alicyclic carboxaldehydes include cyclohexanecarboxaldehyde, 2-, 3- or 4-methylcyclohexanecarboXaldehyde, cyclopentanecarboxaldehyde, 3-isopropyl-1-methylcyclohexanecarboxaldehyde, 2,2,6-trimethylcyclohexanecarboxaldehyde, 2,4,6-tripropylcyclohexanecarboxaldehycle, 4-vhexylcyclohexanecarboxaldehyde, etc.

The presently useful benzenoid aldehydes may be aliphatic-aromatic or purely aromatic aldehydes which may or may not be further substituted, e.g.,

benzaldehyde,

o-, mor p-tolualdehyde, phenylacetaldehyde,

2,3- or 2,S-dipentylbenzaldehyde, .1- or 2-naphthaldehyde, biphenyl-4-carboxaldehyde, 2,3-dimethylbenzaldehyde, 4-dodecylbenzaldehyde,

2-, 3- or 4-butylbenzaldehyde, 3-phenylpropi0naldehyde, 4-tolylacetaldehyde,

2-, 3- or 4-ethylbenzaldehyde, 5-tert-butyl-m-tolualdehyde, 2-p-cymenecarboxaldehyde, 6-methyl-2-naphthaldehyde, 2-butyl-l-naphthaldehyde, 4-methyl-4-biphenylcarboxaldehyde, etc.

Ketones, generally, are not as reactive as the aldehydes with the trivalent phosphorus esters and trivalent phosphorus halides. While a wide variety of aldehydes can be used to prepare the presently employed gasoline ad- .juvants, only acetone, 2-propanone and cyclohexanone appear to undergo the reaction.

Triorgano phosphites which are generally useful with the aldehyde and the phosphorus halide to give the presently useful esters may be simple or mixed phosphites. Examples of useful phosphites are trimethyl, triethyl, triisopropyl, tri-n-propyl, tri-n-butyl, tri-tert-arnyl, tri-nheXyl, tri-n-heptyl, tris(2-ethylhexyl), triisooctyl, tri-noctyl, trinonyl, tridecyl, triundecyl, tri-tert-dodecyl, amyl diethyl, butyl di-n-propyl, n-dodecyl dimethyl, ethyl octyl propyl, tris(2-chloroethyl), tris(3-chloropropyl), tris(2-chloropropyl), tris(3,4-dichlorobutyl), tris(2-octafluorohexyl), tris(2-bromoethyl), tris(3-i0dopropyl), tris- (Z-fluoroethyl), tris(dichlorododecyl), tris(2-ethylhexyl), 2-chloroethyl diethyl, 3-bromopropyl bis(2-chloroethyl), diamyl trichlorooctyl, 2-chloroethyl 3-chloropropyl 4- chlorobutyl, 2-chloroethyl methyl propyl, tris(2,3-dichloropropyl), tris(2-bromo-3-chloropropyl), tris(decachlorododecyl) and tris(2-bromo-4-iodobutyl) phosphite.

Instead of the tribasic phosphites there may be employed as the trivalent phosphorus ester component a diester of a hydrocarbyl or halohydrocarbylpho'sphonite, e.g., a compound of the formula hydrocarbyl-P(O-alkyl) or those in which either the hydrocarbyl or the alkyl radical or both contain halogen as substituent. Presently useful phosphonites include, e.g.

dimethyl phenylphosphonite,

diethyl propylphosphonite,

ethyl methyl phenylphosphonite,

di-n-propyl methylphosphonite,

di-n-butyl a-naphthylphosphonite, bis(2-chloroethyl) p-tolylphosphonite, bis(Z-chloroethyl) hexylphosphonite, bis(2-ethy1hexyl) 2,4-dibromophenylphosphonite, bis(2-bromo-3-chloropropyl) ethylphosphonite, diethyl butylphosphonite,

bis(2-butyloctyl) ethylphosphonite,

di-n-hexyl p-biphenylphosphonite,

diundecyl n-hexylphosphonite, bis(trichloropropyl) 4-chlorophenylphosphonite, diethyl pentachlorophenylphosphonite,

17 dihexyl xylylphosphonite, dipentyl Z-ethylhexylphosphonite, bis(2-chloroethyl) phenylphosphonite, bis tetrachloropentyl) ethylphosphonite, bis(3-br0mopropyl) biphenylylphosphonite, bis(2,3-dichloropropyl) methylphosphonite, bis(2-iodoethyl) phenylphosphonite, bis(2-bromo-3-chloropropyl) phenylphosphonite, ethyl propyl 2,4-dichlorophenylphosphonite, bis(trichlorooctyl) hexylphosphonite, bis(4-fluorobutyl) biphenylylphosphonite, bis(4-chlorobutyl) ethylphosphonite, bis(dichlorohexyl) phenylphosphonite, bis(2-chlor0propyl) n-butylphosphonite, di-n-butyl pentachlorophenylphosphonite, etc.

Presently useful also as the triorgano phosphorus ester component are phosphinites of the formula (hydrocarbylhPO-alkyl or those in which either the hydrocarbyl or the alkyl radicals or both contain halogen substitution, e.g., the alkyl dihydrocarbylphosphinites such as ethyl, allyl, butyl, n-octyl diethylphosphinite or diphenylphosphinite or phenyl-u-naphthylp-hosphinite or biphenylylphenylphosphinite; the corresponding haloalkyl esters such as 2-chloro-propyl diphenylphosphinite or 2- fiuoroethyl ethylmethylphosphinite; and the corresponding esters of the halo-substituted phosphinic acids such as the methyl, pentyl, ethyl, butyl, dodecyl, 2-chloroethyl, 3-bromopropyl or trifiuoropentyl esters of =bis(4-chloropheny1)phosphinite or of n-butyl(4-bromobutyl)phosphinite.

An alkyl radical present in the phosphite, phosphonite or phosphinite may also be one derived from a branchedchain alcohol obtained according to the x0 process by the reaction of carbon monoxide and hydrogen with a higher olefin, e.g., butylene dimer or propylene trimer.

The presently useful phosphorus compounds, as already disclosed, are very conveniently prepared from the trivalent phosphorus-pentavalent phosphorus esters that are prepared by mixing together an aldehyde and the mixture of phosphorohalidite and phosphite which is obtained by reacting phosphorus trichloride or phosphorus tribromide with an oxirane compound.

Oxirane compounds suitable for reaction with the phosphorus trichloride or phosphorus tribromide to yield mixtures of phosphite and phosphorochloridite that are reacted with an aldehyde to give the compounds which are presently isomerized are, e.g., ethylene oxide and alkyl derivatives thereof such as propylene oxide, isobutylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2- epoxypentane, 2,3-epoxypentane, 2,3-epoxyhexane, 1,2- epoxyhexane, 1,2-epoxyheptane, 2,3-epoxy-3-ethylpentane, 1,2 epoxy 4 methylpentane, 1,2 epoxy 2- ethylhexane, 1,2 epoxy 2,4,4 trimethylpentane, 1,2: epoxy 2,3 dimethylheptane; haloalkyl-substituted 0X1- ranes such as epichlorohydrin, epibromohydrin, epiiodohydrin, epifluorohydrin, 1,2 epoxy 4 bromobutane, 2,3 epoxy 4 chlorobutane, 1,2 epoxy 3,4 dibromobutane, 2,3 epoxy 1 bromopentane, 3,4 epoxy- 2 chlorohexane, 1,2 epoxy 3,3,3 trifluoropropane, 1 bromo 2,3 epoxyheptane.

Reaction of two moles of phosphorus trichloride or of phosphorus tribromide with five moles or with more than four but less than five moles of the presently useful substituted oxiranes gives, by way of example, mixtures of the following phosphites and phosphorohalidites which are advantageously reacted with an aldehyde to give presently useful lubricant adjuvants:

Tris(2 chloroethyl) phosphite and bis(2 chloroethyl) phosphorochloridite,

Tris(2,3-dichloropropyl) phosphite and bis(2,3-dichloro propyl) phosphorochloridite,

Tris(2-chloropropyl) phosphite and bis(2-chloropropyl) phosphorochloridite,

Tris(2-bromoethyl) phosphite and bis(2-brom-oethyl) phosphorobromidite,

Tris(Z-bromopropyl) phosphite and bis(2-bromopropy1) phosphorobromidite,

Tris(2,3-dibromopropyl) phosphite and bis(2,3-dibromopropyl) phosphorobromidite,

Tris(3-bromo-2-chloropropyl) phosphite and bis(3- bromo-Z-chloropropyl) phosphorochloridite,

Tris(Z-bromo-S-chloropropyl) phosphite and bis(2- bromo-3-chloropropyl) phosphorobromidite,

Tris(Z-chlorobutyl) phosphite and bis(2-chlorobutyl) phosphorochloridite,

Tris(Z-bromohutyl) phosphite and bis(2-bromobutyl) phosphorobromidite,

Tris(Z-chloro-l-methylpropyl) phosphite and bis(2- chloro-l-methylpropyl) phosphorochloridite,

Tris[(l-chloromethylybutyl] phosphite and bis[(1- chloromethyDbutyl] phosphorochloridite,

Tris[(l-brornomethyD-tert-amyl] phosphite and bis l-brom-omethyl) -tert-amyl] phosphorobromidite.

Since reaction of the oxirane compound with the phosphorus trihalide proceeds through opening of the oxirane ring, there may be present in the above mixtures minor amounts of isomeric phosphite and isomeric phosphorohalldite, e.g., while in the reaction of phosphorus trichloride and propylene oxide and the oxirane ring opens with preferentlal formation of tris(Z-chloropropyl) phosphite and bis(2-chloropropyl) phosphorochloridite, there may also be formed small quantities of bis(1-methyl-2-chloroethyl) phosphite and bis(I-methyl-Z-chloroethyl) phosphorochloridite. The iso-rner content, if any, of the reaction mixture is of no consequence for the present purpose because the isomers also react with the carbonyl compound to give phosphite-phosphonates. While the small quantity of isomeric ph-osphite-phosponate present in the final reaction product may be considered to constitute an impur-ity, it is not detrimental in practical application, for the isomers are so closely related that they possess substantially the same utility insofar as lubricant adjuvant use is concerned.

Reaction of any of the above phosporus-halogen compounds with any of the aldehydes or ke-tones dicloscd above and any of the triorgano trivalent phosporus compounds gives products which are useful per se as adjuvants for lubricant compositions, and such products may be further reacted with oxygen or sulfur or heat-isomerized as shown hereinbefore. Examples of presently useful lubricant additives which are prepared from a substantially equimolar mixture of phosporus-halogen compound, carbonyl compound and trivalent phosphorus ester are:

Tris-[a(di-n-hexyloxyphosphinyl)benzyl] phosphite prepared from tri-n-hexyl phosphite, benzaldehyde and phosphorus trichloride;

Tris{ 1- [bis (2-chloroethoxy)phosphinyl]-propyl}phos- :phite prepared from tris(2chloroethyl) phosphite, propionaldehyde and phosphorus trichl oride;

Tris{ l [bis (2-chloroethoxy) phosphinyl] -ethyl}ph osphite prepared from phosphorus trichloride, tris (2- chloroethyl) phosphite and acetaldehyde;

Tris[Z-diethoxyphosphinyl-Z-propy1] phosphite prepared from acetone, ttriethyl phosphite and phosphorus trichloride;

Bis{ 1- bis (Z-chloroeth oxy phosphinyl] propyl}phenylphosphonite prepared from tris(Z-chloroethyl) phosphite, phenylphosphonous dichloride and propionaldehyde;

Bis adihexyloxyphosphinyl) benzyl] phenylphosphonite prepared from phenylphosphonous dichloride, tri-hexyl phosphite and benzaldehyde;

Bis 1-(diethoxyphosphinyl)propyl] n-butylphosph-oni-te prepared from triethyl phosphite, propionaldehyde and n-butylphosphonous dichloride;

Bis{ 1- [bis (Z-chloroethoxy phosphinyl] ethyl}phenyl phosphite prepared from acetaldehyde, tris(2-chloroethyl) phosphite and phenyl phosphorodichloridite;

Bis[ l-dimethoxyphosphjnyl) ethyl] S-p-chlorophenyl phosphorothioite prepared from acetaldehyde, trimethyl phosphite and p-chlorophenyl phosphorodichloridothioite;

Bis[1-(diethoxyphosphinyDethyH ethyl phosphite prepared from triethyl phosphite, acetaldehyde and ethyl phosphorodichloridite;

Bis[a-(diethoxyphosphinyl)benzyl] ethyl phosphite prepared frorn benzaldehyde, triethyl phosphite and ethyl phosphorodichloridite;

1-(diethoxyphosphinyDpropyl diphenyl phosphite prepared from triethyl phosphite, diphenyl phosphorochloridite and propionaldehyde;

1-[his(2-chloroethoxy)phosphinyl]ethyl dip'henyl phosphite. prepared from acetaldehyde, tris (2-chloroethyl) phosphite land diphenyl phosphoroehloridite;

1-[bis(2-ethylhexyloxy)phosphinyl]benzyl diphenyl p'hosphite prepared from d-ip'henyl phosphorochloridite, tris(Z-ethylhexyl) phosphite and benzaldehyde;

1- (diethoxyphosphinyl) propyl S,S-bis (4-chlorophenyl) phosphorodithioite prepared from triethyl phosphite, bis(p-chlorophenyl) phosphorochloridodithioite and propionaldehyde;

1-(dieth0xyphosphinyl)propyl diphenylpho sphinite prepared from diphenylphosphinous chloride, triethyl phosphite and propionaldehyde;

u-[Bis(2-chloroeth0xy)phosphinyl]benzyl bis(2 chloroethyl)phosphite prepared from rtris(2-ehlor0ethyl)phosphite, bis(2-chloroethyl)phosphoroehloridite and benzaldehyde;

1- [bis 2-chloropr-op oxy) phosphinyl propyl bis 2-chloropropyl phosphite prepared from bis(2-chloropropyl) phosphorochloridite, tris(Z-chloropropyl) phosphite and propionaldehyde;

1-[bis(2-bromo-3-chloropropoxy)phosphinyllethyl bis(2- brom o 3 chloropropyl) phosphite prepared from tris(2-bromo-3-chloropropyl) phosphite, bis(2-br0rno- 3-chloropropyl) phosphorobromidite and acetaldehyde;

1- [bis(2-bromopropoxy)phosphinyl] propyl bis(2bromopropyDphosphite prepared from tris(Z-bromopropyl) phosphite, bi s(2-bromopropyDphosphorobromidite and propionaldehy-de;

1- [bis( 2,3-dichloropropoxy) phosphinyl] -2-phenylethyl bis (2,3-dichloropropyl) phosphite prepared from phenylacetaldehyde, bis(2,3-dichlropropyl) phosphorochloridite and tris(2,3-dichl0ropropyl) phosphite;

1- [bis 2,3-dichloropropoxy) phosphinyl propyl bis 2,3-dichloropropyl) phosphite prepared from bis(2,3-dichloropropyl) phosphorochloridite, tris(2,3-dichlor0pr0-t pyl) phosphite and propionaldehyde;

1- [bis'( 2-chloroethoxy) phosphinyl] ethyl bis (2-chloroethyl) phosphite prepared from bis(2-chloroethyl) phosphorochloridite, tris(Z-chloroethyl) phosphite and acetaldehyde;

1- [bis 2-chloroethoxy) phosphinyl] propyl bis (2-chlor oethyl) phosphite prepared from bis(2-chloroethyl) phosphorochloridite, tris(2-chlor0ethyl) phosphite and propionaldehyde;

1- [bis 2-chloroethoxy) phosphinyl] butyl bis (2-chloroethyl)phosphite prepared from bis(2-chloroet hyl) phosphorochloridite, tris(2-chloroethyl) phosphite and n-butyraldehyde;

1- [-bis 2-chloroethoxy phosphinyl] -2-ethylhexyl bis( 2- chloroethyl) phosphite prepared from Z-ethylhexaldehyde, bis(2-chloroethyl) phosphorochloridite and tris (2-chloroethyl) phosphite;

1- [bis (2-chloroethoxy phosphinyl undecyl bis Z-chloroethyl) phosphite prepared from bis(2-chloroethyl) phosphorochloridite, tris(Z-chloroethyl) phosphite and undecylaldehyde;

OL- [Bis 2-chl0r0eth0xy phosphinyl] benzyl bis 2-chloroethyl) phosphite prepared from benzaldehyde, bis(2- chloroethyl) phosphorochloridite and tris(Z-chloroethyl) phosphite;

a- [Bis 2-chloroethoxy) phosphinyl] -4methylbenzyl bis (2-chloroethyl) phosphite prepared from bis(2-chloroethyl) phosphorochloridite, tris(2-chloroethyl) phosphite and 4-tolualdehyde;

1- [bis Z-chloroethoxy) phosphinyl1cycl0hexyl bis(2-chloroethyl) phosphite prepared from his(2-chloroethyl) phosphorochloridite, tris(2-chloroethyl) phosphite and cyclohexanone;

[Bis 2-chloroethoxy phosphinyl methyl bis (2-ch1oroethyl) phosphite prepared from tris(2-chloroethyl) phosphite, bis(2-ch1oroethyl) phosphorochloridite and formaldehyde;

2- [bis Z-chloroethoxy phosphinyl] butyl bis 2-chloroethyl) phosphite, prepared from tris(2-chloroethyl) phosphite, bis(2-chloroethyl) phosphorochloridite and methyl ethyl ketone;

1- [bis 2-chloroethoxy phosphinyl] propyl bis (Z-chloro- 2-phenylethyl) phosphite prepared from bis(2-chlor0- 2-phenylethyl) phosphorochloridite, tris(2-chloroethyl) phosphite and propionaldehyde;

2- [bis 2-chloropropoxy phosphinyl] propyl bis 2-chlor0- propyl) phosphite prepared from bis(2-chloropropyl) phosphorochloridite, tris(Z-chloropropyl) phosphite and acetone;

1- [bis Z-chloropropoxy phosphinyl] ethyl bis 2-chloropropyl) phosphite prepared from tris( 2-ch1oropropyl) phosphite, bis(2-chloropropyl) phosphorochloridite and acetaldehyde;

2-[ l- (dimethoxyphosphinyl) ethyloxy] -4,5-benzo-l ,3 ,2-

dioxaphospholane prepared from trimethyl phosphite, acetaldehyde and 2-chloro-1,3,2-benzodioxaphosphole;

2- l-(diethoxyphosphinyl)ethoxy] -1,3,2-dioxaphospholane prepared from triethyl phosphite, acetaldehyde and 2-chloro1,3,2-dioxaphospholane;

2-[ 1:(dibutoxyphosphinyl)ethoxy1-1,3,2-dioxaphospholane prepared from tributyl phosphite, 2-chloro- 1,3,2-di0xaphospholane and acetaldehyde;

2-{ 1- [bis 2-chloroethoxy phosphinyl] ethoxy}- l ,3 ,2-

dioxaphospholane prepared from tris(2-chloroethyl) phosphite, 2-chloro-1,3,2-dioxaphospholane and acetaldehyde;

2-[ l-(diethoxyphosphinyl)propoxy]-1,3,2-dioxaphosphorinane prepared from2-chloro-1,3,2-dioxaphosphorinane, triethyl phosphite and propionaldehyde;

2-[1-(dirnethoxyphosphinyl)propoxy]-4-chloromethyl- 1,3,2-dioxaphospholane prepared from propionaldehyde, trimethyl phosphite and 2-chloro-4-ehloromethyl- 1,3,2-di0Xa-phosph0lane;

2-[ 1-(diethoxyphosphinyl)butoxy]-1,3,2-dioxaph0spholane prepared from triethyl phosphite, 2-chloro- 1,3,2-di0xaphospholane and butyraldehyde;

2-[ l-(diethoxyphosphinyl) -2-ethylhexyloxy] -1,3,2-dioxaphospholane prepared from triethyl phosphite, 2-chloro-1,3,2-dioxaphospholane and Z-ethylhexaldehyde;

2 1- bis Z-chloroethoxy phosphinyl] -2-ethylhexyloxy}- 4-chlor0rnethyl-1,3,2-dioxaphospholane prepared from tris(Z-chloroethyl) phosphite, 2-chloro-4-chloromethyl- 1,3,2-dioxaphospholane and 2-ethylhexaldehyde;

2-[ct-dimethoxyphosphinyl)benzyloxy]-1,3,2-dioxaphospholane prepared from benzaldehyde, trimethyl phosphite and 2-chlor0-1,3,2-dioxaphospholane;

2-[a-(diethoxyphosphinyl)benzyloxy] -4,5-benzo-1,3,2-di-- oxaphospholane prepared from 2-chlor0-l,3,2-benzodioxaphosphole, triethyl phosphite and benzaldehyde;

2- [oc- (diethoxyphosphinyl benzyloxy] -4-chloromethylv 1,3,2-dioxaphospholane prepared from triethyl phos-- phite, .2-chloro-4-chloromethyl-1,3,2-di0xaph0spho1ane I and benzaldehyde;

2- [adimethoxyphosphinyl naphthoxy] -4-chlor0methy1- 1,3,2-di0xaphospholane prepared from l-naphthaldehyde, trimethyl phosphite and 2-chloro-4-chloromethyl-r 1,3,2-dioxaphospholane;

21 2-[2-(dimethoxyphosphinyl)propoxy]-1,3,2-dioxaphospholane prepared from trimethyl phosphite, 2-cl1loro- 1,3,2-dioxaphospholane and acetone;

2-[ 1- diethoxyphosphinyl cyclopentyloxy] l ,3,2-dioxaphospholane prepared from triethyl phosphite, 2-chloro-l,3,2-dioxaphospholane and cyclopentanone;

2-[ 1- dimethoxyphosphinyl cyclohexyloxy] -4,5-benzo- 1,3,2-dioxaphospholane prepared from trimethyl phosphite, cyclohexanone and 2-chloro-1,3,2-benzodioxaphosphole;

2-[ 1- (diethoxyphosphinyl cyclohexyloxy] 1,3,2 dioxaphospholane prepared from triethyl phosphite, 2-chloro-1,3,2-dioxaphospholane and cyclohexanone;

2-[ ldihexyloxyphosphinyl cyclohexyloxy] -4,5-benzo- 1,3,2-dioxaphospholane prepared from 2-chloro-1,3,2- benzodioxaphosphole, tri-n-hexyl phosphite and cyclohexanone;

2-{ l- [bis 2-chloroethoxy phosphinyl] cyclohexyloxy}-4,5- benzo-l,3,2-dioxaphospholane prepared from cyclohexanone, tris(2-chloroethyl) phosphite and 2-chloro-l,3,2- benzodioxaphosphole;

l-[bis(2-chloropropoxy)phosphinyl]heptyl bis (2-chloropropyl) phosphite prepared from bis(2-chloropropyl) phosphorochloridite, tris(2-chloropropyl) phosphite and phosphite and heptaldehyde;

oc- [Bis 2-chloropropoxy phosphinyl] benzyl bis 2-chloropropyl) phosphite prepared from bis(Z-chloropropyl) phosphorochloridite, tris(2-chloropropyl) phosphite and benzaldehyde;

2- [2- (diethoxyphosphinyl)propoxy] -1,3,2-dioxapl1ospho1- ane prepared from triethyl phosphite, acetone and 2- chloro-1,3,2-dioxaphospholane;

Bis[a-(dihexyloxyphosphinyl)benzyl]phenyl-phosphonite prepared from phenylphosphonous dichloride, trihexyl phosphite and benzaldehyde;

Bis l-diethoxyphosphinyl )propyl1propyl] n-butylphosphonite prepared from triethyl phosphite, propionaldehyde and n-butylphosphonous dichloride;

Tris 1- ethoxyphenylphosphinyl ethyl] phosphite prepared from diethyl phenylphosphonite, phosphorus trichloride and acetaldehyde;

Bis 1-(ethoxyphenylphosphinyl propyl] phenyl phosphite prepared from diethyl phenylphosphonite, propionaldehyde and phenyl phosphorodichloridite;

2 [l-(ethoxybutylphosphinyDpropyloxy] -4,5-benzo-1,3,2- dioxaphosp'h olane prepared from diethyl butylphosphonite, propionaldehyde and 2-chloro-4,5-benzo-l,3,2- dioxaphospholane;

Bis [I- ethoxyphenylphosphinyl ethyl] phenylphosphonite phepared from diethyl phenylphosphonite, phenylphosphonous dichloride and acetaldehyde.

The invention is further illustrated by, but not limited to, the following examples:

EXAMPLE 1 To 226.1 g. (0.4 mole) of a substantially equimolar mixture of tris(2-chloropropyl)phosphite and bis(2-chloropropyl) phosphorochloridite, there was added, with cooling, 20.7 g. of acetaldehyde (0.44 mole) at a temperature of 10--13 C. during 10 minutes. When all of the aldehyde had been added, cooling was discontinued and the reaction mixture was stirred for 0.3 hour. During this time the temperature reached 85 C. before cooling brought it under control. The reaction mixture was then warmed at 85 C. to insure complete reaction, then placed under vacuum and concentrated to remove material boiling below 120 C./0.7 mm. There was thus obtained as residue 198.6 g. (100% theoretical yield) of the substantially pure bis(2-chloropropyl) phosphite of bis(Z-chloropropyl) (l-hydroxyethyl)phosphonate n 1.4782 of the structure CH (ou ouoloHzonPm lm-i (OOHZOHCIOH Z and analyzing as follows:

Found Calcd. for

C HzaC140i3P7 Percent C 33. 66 33.86 Percent H 5. 96 5. 68 Percent Cl 28. 28. 51

EXAMPLE 2 To 198 g. of an equimolar mixture consisting of bis- (2-chloroethyl) phosphorochloridite and tris(2-chloroethyl) phosphite there was added, with cooling during 0.2 hour, 68.2 g. (0.4 mole) of undecylaldehyde. After all of the aldehyde had been added, cooling was discontinued and the temperature of the reaction mixture increased spontaneously to 40 C. Concentration to a pot temperature of 148 C./0.2 mm., gave as residue 226.0 g. (100% theoretical yield) of the substantially pure bis(2-chloroethyl) phosphite of bis(Z-chloroethyl) (l-hydroxyundecyl)phosphonate, 11 1.4808, of the structure (C1CH2CH20)2POCH (OCHZCHZCDI (CH2)9CH3 The presently provided phosphonate analyzed as follows:

Calcd. for Found CmHaaCliOn Percent C 39. 77 40. 3 Percent H 6.72 6. 8 Percent 01 25. 15 25. 1

EXAMPLE 3 I a s EXAMPLE 4 2-chloro-1,3,2-benzodioxaphosphole (69.8 g., 0.4 mole) was added, during 15 minutes, to a mixture consisting of 134 g. (0.4 mole) of tri-n-hexyl phosphite and 39.3 g. (0.4 mole) of cyclohexanone. During addition of the phosph ole, the temperature of the reaction mixture was maintained at 2530 C. by occasional cooling. The whole was then stirred until cessation in temperature rise, employing external cooling in order to maintain the temperature of the mixture at below 40 C. The reaction was completed by heating the mixture to 95 C.; and byproduct n-hexyl chloride was removed by heating the mixture to C. under water-pump vacuum. Concentration to 168 C./0.4 mm., gave as residue 189.5 g. (99.6% yield) of the substantially pure pyrocatechol phosphite (cyclic ester) of di-n-hexyl (l-hydroxycyclohexyl) phosphonate, 11 1.4970, analyzing 58.55% carbon and 23 8.80% hydrogen as against 59.21% and 8.27%, the calculated values, and having the structure EXAMPLE 5 To a mixture consisting of 59.9 g. (0.36 mole) of triethyl phosphite and 91.0 g. (0.36 mole) of diphenyl phosphorochloridite, there was added, dropwise, 21.0 .g. (0.36 mole) of propionaldehyde. The temperature rose exothermally to 38 C., at which point ice-cooling was applied and the remainder of the aldehyde was added while maintaining the temperature at firom 20-25 C. When all of the aldehyde had been added, the reaction mixture was heated to 70 C. in order to insure complete reaction. By-product ethyl chloride and any unreacted material were removed by placing the reaction mixture under water-pump vacuum and heating it to 100 C. Concentration to a pot temperature of 176 C./0.2 mm., gave as residue 139.5 g. (94% theoretical yield) of the substantially pure diphenyl phosphite of diethyl (l-hydroxypropyl)phosphonate, 11 1.5222, analyzing 55.00% carbon and 6.48% hydrogen, as against 55.39% and 6.36%, thecalculated values, and having the structure CaH5- C aH5- C 2H5 EXAMPLE 6 Triethyl phosphite (26.6 g., 0.16 mole) was added to a solution of 49.5 g. (0.14 mole) of bis(p-chlorop1henyl)- phosphorochloridodithioite in 75 ml. of benzene. To the resulting mixture there was gradually added, with cooling, 11.6 g. (0.2 mole) of propionaldehyde. The temperature of the reaction mixture during the addition of the aldehyde was maintained at from 18 C. to 35 C. When all of the aldehyde had been added, the mixture was warmed to 44 C. and an additional 1g. portion of the propi'onaldehyde was added. This caused a rapid rise to 47 C. The reaction mixture was then refluxed (68-75 C.) for 0.5 hour, cooled to 25 C., and concentrated to a pot temperature of 105 C./0.l mm, to give 75.1 g. (theory, 71.8 g.) of the substantially pure bis(S-pchlorophenyl)phosphorodithioite of diethyl ('1- hydroxyp-ropyl)phosphonate, analyzing 14.23% Cl and 11.66% S .as against 13.8% and 12.5%, the calculated values for C H Cl O P S and having the formula 0 [I (Ck-@Sh-P-O-GHEFT-(OOHzCHa)2 CHzCHs EXAMPLE 7 24 I and 7.05%, the respective calculated values, and having the structure CHsO CH3 0 POC-] (OCH2OHa)2 EXAMPLE 8 The bis(2-chloropropyl)phosphite of bis(2-chloropropyl) 1 hydroxypropyl)phosphonate (I) was prepared by mixing together substantially equimolar proportions of bis(2-chloropropyl)phosphorochloridite, propionalde- 'hyde and tris(2-chloropropyl)phosphite and volatilizing off the by-product propylene dichloride. The residual p'hosphite-phosphonate was then heated at 180-200 C.

CHaO

This example describes the production of a phosphitediphosphonate by reaction of acetaldehyde with a mixture of phosphite and phosphorochloridite prepared from two moles of phosphorus trichloride and 4.75 moles of propylene oxide, and isomerization. of the phosphitediphosphonate to the triphosphonate.

The mixture of phosphite and phosphorochloridite was prepared as follows: A 2-liter flask was charged with 550 g. (4.0 moles) of phosphorus tric-hloride and 2.75 g. of ethylene ehlorohydrin. It was immersed in a Dry Ice bath and 552 g. (9.5 moles) of propylene oxide was added thereto during 20 minutes at a temperature of 1020 C.

After removing a 6.0 g. sample of the resulting reaction mixture, the remaining reaction product, consisting of one mole of tris(2-chloropropyl) phosphite per two moles of bis(2-chloropropyl) phosphorochloridite, was treated with 127 g. of acetaldehyde during 5 minutes at a temperature of l8-20 C. When the heat of reaction had subsided (about 0.2 hour after addition of the aldehyde) the reaction mixture was warmed at 90 C. for 0.5 hour. It was then placed under vacuum and was concentrated to a pot temperature of C./ 1.0 mm. to remove byproduct propylene dichloride. There was thus obtained as residue 934 g. of the colorless reaction product, 11 1.4797, of which two-thirds in moles consisted of a polyphosphonate-phosphite of the formula 7 in I 3 1| (CH CHCI CHZO)2P OOH --I?"-OCH--P(OCH2CHClCH )z CH CHClCH2O L wherein n is one, with the balance being a compound of the above formula wherein n is zero.

A 300 g. sample of the reaction product was isomerized to the triphosphonate by heating under vacuum with stirring to C./O.2 mm. and maintaining at 195-205" C./0.2 mm. for 0.5 hour. There was thus obtained as residue a mixture of triphosphonates of the formula 0 on. 311, I $1) ortaolrclol-no-PooIr----P--o--oH -P(OOHzCHC1CH )z OH GH I..

wherein for two-thirds of the mixture the value of n is one, and for one-third of said mixture the value of n is zero. Nuclear magnetic resonance spectra showed that 25 the phosphorus had been completely converted to the pentavalent state.

EXAMPLE The bis(2-chloropropyl) phosphite of bis(2-chloropropyl) (1-hydroxy-2-ethylhexyl)phosphonate was prepared by mixing together substantially equimolar proportions of bis(Z-chloropropyl) phosphorochloridite, 2-ethylhexanal, and tris/(2-chloropropyl) phosphite. It was oxidized by passing ozone into a methylene chloride solution of 58.0 g. (100 millimoles) of said phosphite-phosphonate at a temperature of 50 C. to 60 C. at a rate of 0.70 millimole minute until the ozone began coming through the solution and into a potassium iodide trap attached to the reaction vessel. To assure complete oxidation, the ozone was maintained for an additional minute or so until the characteristic blue color of ozone was apparent in the reaction vessel. Excess ozone was then sparged out with nitrogen and the solution was allowed to warm to room temperature. The methylene chloride was then removed by heating the solution under water-pump vacuum, and the residue was held at 100 C. under vacuum for about an hour. There was thus obtained 59.7 g. of the substantially pure 1-[bis(2-chloropropoxy)phosphinyl]-2-ethylhexyl bis(Z-chloropropyl) phosphate of the formula (omonolomoni oou i (oouzonoiortm CHC2H5 (ormaom EXAMPLE 11 A mixture consisting of 510.2 g. (1.0 mole) of the bis(2-chloropropyl) phosphite of bis(Z-chloropropyl) (1- hydroxypropyl)phosphonate, prepared by reacting together a substantially equimolar mixture of bis(2-chloropropyl) phosphorochloridite, propionaldehyde and tris-(2- chloropropyl) phosphite, and 24.0 g. of sulfur flowers was warmed to about 50 C., at which point a mildly exothermic. reaction was noted. Cooling was applied for a few minutes to keep the temperature below 80 C. The whole was then heated at 120 C. for one hour, at which point another 4.8 g. of sulfur was added and heating was continued at 110 C.-130 C. for 0.5 hour. At the end 26 (dihexyloxyphosphinyl)benzyl] phosphorothioate of the EXAMPLE 13 This example describes the preparation of a phosphitediphosphonate by reaction of acetaldehyde with a mixture of phosphite and phosphorochloridite prepared from 16.0 moles of phosphorus trichloride and 37.36 moles of propylene oxide, and the thionation of the phosphitediphosphonate to the phosphorothioate-diphosphonate.

The mixture of phosphit and phosphorochloridite was prepared as follows: A 5-liter flask equipped with a glass and Teflon stirrer, thermometer, water condenser (protected) and a dropping funnel extending below the liquid surface was swept with nitrogen and charged with 2200 g. (16.0 moles) of phosphorus trichloride and 16.5 g. of thylene chlorohydrin. The flask was cooled in a Dry-Ice bath as 2167 g. (37.36 moles) of propylene oxide was added below the surface at 25*30 C. in 0.9 hr.

After removing a 6.0 g. sample of the resulting reaction mixture, the remainder, consisting of one mole of tris(2-chloropropyl) phosphite per two moles of bis(2- chloropropyl) phosphorochlorodite, was treated with 516 g. (10.64 moles+10% excess) of acetaldehyde in 0.4 hr. After th heat of reaction had subsided, the reaction mixture was warmed at 80-90 C. for 0.5 hr., cooled to C., and then concentrated to 125 C./0.01 mm. to give 1224 g. of propylene dichloride and excess acetaldehyde in a Dry Ice trap and 3624 g. of a viscous, colorless, clear residue, 111325 1.4812, having the formula wherein n has an average value of 1. Cryoscopic molecular weight determination of the product gave a value of 694 as compared to 680, the theoretical value.

Approximately 3400 g. of the above material was treated with 120.2 g. of flowers of sulfur at 50 C. The temperature of the mixture increased spontaneously to 96 C. The mixture was warmed to 140 C. (the reaction mixture became clear at 130 C.), and finally concentrated to 140 C./0.01 mm. to obtain 3516 g. of a of this time another 25.5 g. of the phosphite-phosphonate 50 clear, colorless liquid, 11 1.4869, having the formula starting material was added and heating was continued for a few minutes until the yellow color disappeared. The colorless reaction mixture was then concentrated to 160 C./0.5 mm. to give 560 g. of the 0,0-bis(2-chloropropyl) phosphorothioate of bis(Z-chloropropyl) (l-hydroxypropyDphosphonate of the formula.

(omonolonzo 1 0 crrf oornorroio H3).

CHZCH;

EXAMPLE 12 CH3 OCHzCHClOI-I CH wherein n has an average value of 1. Cryoscopic molecular weight determination of the product in benzene gave a value of 737 as compared to 712, the theoretical value. Nuclear magnetic measurements showed that the trivalent phosphorus of the phosphite-polyphosphonate intermediate was converted to the pentavalent state.

EXAMPLE 14 To a cooled mixture consisting of 140 g. (0.56 mole) of tributyl phosphite and 67.3 g. (0.53 mole) of 2-chloro- 1,3,2-dioxaphospholane there was added dropwise, with stirring, 28.2 g. (0.64 mole) of acetaldehyde. During addition of the aldehyde, which required about 12 minutes, the temperature of the reaction mixture rose from 2 C. to 25 C. When all of the aldehyde had been added, the whole was warmed to 65 C., but no further reaction was evidenced. It was then warmed to C. to remove any volatile impurities and by-product, and the residue was distilled to give 134.6 g. of the substan- II S P-OCH-P (O Bu):

Reaction was effected by adding 4.5 g. of sulfur to 62.7 g. (0.19 mole) of (I) at room temperature, heating the resulting mixture to 115 C., adding 1.0 g. of sulfur, heating this to solution, and finally adding another 0.6 g. of the sulfur to make a total of 6.1 g. (0.19 mole). The whole was then heated at 1'20-130 C. for 40 minutes. There was thus obtained 68.1 g. (99% theoretical yield) of (II), i.e., 2 [l-(dibutoxy-phosphinyl)ethoxy] thio- 1,3,2-dioxaphosphol'ane.

EXAMPLE a 1- [*bis (Z-choropropoxy) phosphinyl] heptyl bis 2-chloropropyl) phosphite was prepared by reacting n-heptaldehyde with an equimolar mixture of bis(2-chloropropyl) phosphorochloridite and tris(2-chloropropyl) phosphite.

EXAMPLE 16 A 566.2 g. (1.00 mole) portion of l-[bis(2-chloropropoxy)phosphinyl]heptyl bis(2-chloropropyl) phosphite, prepared by reacting n-heptaldehyde with an equimolar mixture of bis(.2-chloropropy1) phosphorochloridite and .tris(2-chloropropyl) phosphite, and 25.6 g. of sulfur were placed in a 1 liter flask and stirred and warmed. At about 55 C. an exothermic reaction started and the temperature increased spontaneously to 105 C. The sulfur was not all dissolved as yet so the reaction mixture was then warmed to 160 C. The reaction mixture became clear and colorless at 130 C. The liquid was heated to 170 C./1.0 mm. to give 583 g. (99% yield) of a clear colorless liquid, n 1.4824, having the formula To a cooled (0 C.) mixture consisting of 113.7 g. (0.71 mole) of triethyl phosphite and 82.5 g. (0.65 mole) of 2-chloro-1,3,2-dioxaphospholane there was added dropwise, with stirring, during minutes, 70.1 g. (0.715 mole) of cyclohexanone. The temperature of the reaction mixture rose to 23 C. during the cyclohexanone addition. The whole was then warmed to 70 C., subjected to water-pump vacuum, and heated to 95 C. Subsequent distillation gave 169.0 g. (79.7% theoretical yield) of the substantially pure 2-[l-(diethoxyphosphinyl)cyclohexyloxy]-1,3,2-dioxaphospholane B.P. 156158 C./ 0.3 mm., 152-153 C./0.2 mm., n 1.4779, of the structure 28 The presently provided phosphorus ester analyzed as follows:

Calcd. for Found 0121124 6 Percent C 44. 43 44.16 Percent H.-. 7. 55 7. 48 Percent P 18. 76 18. 98

EXAMPLE 18 This example illustrates the utility of the disclosed compounds as extreme pressure additives for lubricant composition.

Representative compositions of thisinvention were evaluated for extreme pressure gear lubricant characteristics in a standard SAE load test machine and compared against the base oil having no additive therein as Well as against a commercial extreme pressure lubricant composition. For this test a 2% solution of the test phosphorus compound in a reference gear oil RGO 10060 is run through the SAE load machine at 500 r.p.m. and the pounds of load required for seizure is compared to the pounds required for seizure in the same machine With referenced standard lubricant compositions. The results were as follows:

Table I Pounds of load for seizure Additive 2%: (lbs) at 500 r.p.m.

Base oil (no additive) Commercial grade chloronaphtha xanthate, sp. gr. approx. 1.19 at 60/60 F., flash point 250 F., viscosity 63 cts. at F., sulfur 11%, chlorine 31% 380 Example 1 500 Example 2 500 Example 4 220 Example 6 500 Example 10 500 Example 11 500 Example 15 480 Example 16 440 Other compounds within scope of invention:

1-[bis(2 chloropropoxy)phosphinyllbutyl bis (2-chloropropyl) phosphite 330 2 PCl ,4.67 propylene oxide, acetaldehyde and sulfur product (prepared according to the procedure of Example 13) 290 1-[bis(2 chloropropoxy)phosphinyl]ethyl bis- (Z-chloropropyl) phosphorothioate 460 1-[bis(2-chloropropoxy)phosphinyl]-2-methy1- propyl bis(2-chloropropyl)phosphite 440 1 dMaximum load tested no seizure by these samples at this EXAMPLE 19 Various phosphinylhydrocarbyloxy phosphorus esters were tested as 1% solutions of the ester in a reference base oil which test samples were run in the 4-ball wear tester for 15 minutes at 708 r.p.m., 266 F., at loads of 15 and 40 kilograms. Average maximum scar diameters for the 3 lower balls on each run is measured.

The reference base oil to which the phosphorus ester additives are added was a solvent extracted coastal distillate having a viscosity at 210 F. of 45 S.U.S. The four-ball testing machine is designed to test lubricants under conditions 'of pressure to determine their film strength characteristics. The machine is so constructed that one steel ball contacts and rotates upon 3 stationary steel balls of identical physical properties. The lubricant being tested is placed upon the contacting surfaces and the desired load is applied upon the single rotating ball. Wear scars appearing upon the 3 stationary balls are measured and averaged, the diameters being a function of the film strength of the lubricant undergoing the test. The results of the test on materials prepared in accordance with the concept of this invention are described in Table II below:

Various phosphorus esters of this invention were tested for anti-oxidant activities according to the following test procedure.

Typical use concentrations of additives are blended in oil, and 100 grams of oil solution placed in a large test tube. Both soluble and metallic catalyst are added, namely, 0.012% iron naphthenate (as FeO) and a 2. inch by 1 /2 inch lead plate which is suspended in the oil phase. A sparger tube is inserted into the oil, and a cold finger condenser mounted on top of the tube to supress foam. The tube is placed in an oil bath maintained at 300 i1 F. and air admitted through the sparger at the rate of 70 l./hr. The oil sample is removed and examined after 20 hours, and the following is reported: acid number (TAN) and change of weight in the lead catalyst.

A blend of 0.75% by weight of the test compound in a mineral base oil, catalyzed by lead plates and iron naphthenate, is heated at 300 F. for 20 hours with air being bubbled vigorously through the mixture. The formation of acid constituents, an indication of oxidation, is measured by loss of weight from the lead plates, and TAN (total acid number: mg. KOH/gram of oil sample required for neutralization).

The results are summarized in the following table:

l TAN Total Acid Number.

Various types of phosphinylhydrocarbyl phosphorus esters of the above described types exhibit properties of 3% being better for some lubricant oil additive purposes than for others. For example, some show very good antioxidant additive properties but are relatively poor extreme pressure additive properties. Some types show utilities for several lubricant purposes. Some of the phosphitephosphonates are valuable as extreme pressure, antiwear, and anti-oxidant additives, e.g. alkyl phosphonate cyclic phosphites, i.e., compounds of the general formula O alk wherein A, alk, and T are as defined above are especially good anti-wear and anti-oxicant additives.

In general, compounds having smaller constituent groups on the phosphorus atoms of these phosphinylhydrocarbyl phosphorus esters, and on the linking carbon atom show improved thermal and oxidative stability but such compounds show decreased wear resistance properties. Antiwear properties improve with increasing size of the linking group, i.e., that group derived from the carbonyl compound reactant. Because of the great possibility of variation of chemical structure in these compounds by starting with various phosphorus chlorides or bromides, carbonyl compounds, and trivalent phosphorus esters in their manufacture, specific compounds can be tailor-made for specific applications. Surprisingly, although it is generally felt in the art that good extreme pressure lubricants additives must have chlorine and/or sulfur in the structure thereof, it has been found that some of the phosphorus additives of this invention, such as 2-[1-(dihexyloxyphosphinyl)-cyclohexyloxy]-4,5 benzo 1,3,2 dioxaphospholane, possess good extreme pressure additive properties even though no chlorine or sulfur appears in such compound. The chloroalkyl phosphinylhydrocarbyl phosphorus esters, especially those derived from the chloropropyl esters, exhibit very good extreme pressure additive properties. In such compounds good extreme pressure properties does not seem to be dependent on the linking group size. In producing extreme pressure additives from these haloalkyl phosphinylhydrocarbyloxy phosphorus esters, bromine may ordinarily be readily substituted for chlorine; however, in special applications, the bromoalkyl derivatives present solubility problems which may require the use of solubilizing agents.

Compositions of this invention can be combined with other additives such as blooming agents, pour-point depressors, and/ or viscosity improvers, anti-foaming agents, and the like. Among the specific additives for lubricating purposes which can be used are oil-soluble detergents which include oil-soluble salts of various bases with detergent-forming acids. Such bases include metal-containing as well as organic bases. Metallic bases include those of alkali metals, Ca, Mg, Cu, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include various nitrogen bases as primary, secondary, tertiary amines and quaternary ammonium compounds, c.g., benzyl trimethyl ammonium hydroxide.

Examples of detergent-forming acids are the fatty acids of say, 10 to 30 carbon atoms, tall-oil acids, rosin acids, wool-fat acids, paraffin-wax acids (produced by oxidation of paraffin Wax), chlorinated fatty acids, aromatic hydroxy fatty acids, paraffin wax benzoic acids, various alkyl salicyclic acids, phthalic acid monoesters, aromatic keto acids, aromatic ether acid diphenols such as di-(alkylphenol) sulfides and disulfides, methylene bis-alklyl phenols; sulfonic acids such as may be produced by treatment of alkyl aryl hydrocarbons or high-boiling petroleum oils with sulfuric acids; sulfuric acid monoesters; phosphoric, arsenic and antimony acid monoand di-esters, including the corresponding thiophosphoric and arsenic acids and the like.

Additional detergents are the alkaline earth phosphate diesters, including the thiophosphate diesters; the alkaline earth diphenolates, specifically, the calcium and barium.

salts of diphenol monoand poly-sulfides.

An excellent detergent for the present purpose is the calcium salt of oil-soluble petroleum sulfonic acids. This may be present advantageously in the amount of about 0.025% to 0.2% sulfate ash. Also, alkaline metal salts of alkyl phenol-aldehyde condensation products are excellent detergents.

Antioxidants which are suitable for use in combination with the phosphinylhydrocarbyloxy phosphorus esters comprise several types, for example, alkyl phenols such as 2,4,6-trimethylphenol, pentamethylphenol, 2,4-dirnethyl-6-tertiary-butyl-phenol, 2,4-dimethyl-6-octylphenol, 2,6 ditertiary-butyl-4-methyl phenol, 2,4,6 tritertiary butylphenol and the like; amino-phenols such as benzylaminophenols; aromatic amines, such as N,N'-dibutyl-p-phenylenediamine, diphenylarnine, phenyl-beta-naphthylamine, phenyl-alpha-naphthylamine, and dinaphthylamine.

Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 or more carbon atoms; alkali metal and alkaline earth salts of sulfonic acids and fatty acids, organic compounds containing an acidic radical in close proximity to a nitrile, nitro, or nitroso group (e.g., alpha-cyanostearic acid), glycidyl phenyl ether, wax disulfide, etc. Additional ingredien-ts may comprise oil-soluble urea or thiourea derivatives, e.g., urethanes, allophanates, carbazides, carbazones, etc., polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high-molecular-weight oil-soluble compounds.

Depending upon the additional additive used and conditions under which it is used, the amount of additive used may vary from 0.01 to 10% or higher. However, substantial improvement is obtained by using amounts ranging from 0.1 to 5.0% in combination with the phosphinylhydrocarbyl phosphorus ester products of this invention.

Typical lubricant oil composition blends for use as motor oils within the scope of this invention are illustrated below:

Parts by Component: v weight 7 (A) Mid-Continent mineral base oil, 10-30 SAE 100 Detergent dispersant, inhibitor type additive,

specified as follows Saybolt Universal viscosity, 55-85 sec. at

210 F., phosphorus OAS-0.55%; sulfur 6%, barium 6.07-6.25 2 Compounds of Example 1 1 Mid-Continent mineral base oil, -30 SAE 100 Anti-oxidant and bearing corrosion inhibia having the following properties: viscosity -25 cts. at 210 F., sp. gr. 1.02 at 60/60 F.,

phosphorous 4.7%, sulfur 13.1% 2

Compound of Example 16 1 Useful gear oil compositions blends having incorporated therein phosphorus esters described herein are illustrated by the following:

Parts by Component: weight Reference gear base oil (Phillips RGO 100 Compound of Example 1 2 The phosphorous ester-containing gear oil lubricant compositions of this invention are compatible with and may incorporate therein Other useful additives, as follows:

Parts by Component: weight- Reference gear base oil (Phillips RGO 100- 60) 100 Chloronaphtha xanthate, sp. gr. approx. 1.19 at 60/60 F., flash point 250 F. min., sulfur 8.1%, chlorine 25%, phosphorus 0.54%---- 7.5 Compound of Example 11 2 What I claim is:

1. A lubricating composition comprising a major amount of a mineral lubricating oil and, based upon said oil a minor amount by weight of a compound of the formula I 1 l LB ll. I

wherein n is a number of 0 to 2, m is a number of 0 to 100 when n is 2 and 0 When n is less than 2, Y is selected from the class consisting of P, EP=O, and EP S, each R is selected from the class consisting of hydrocarbyl, halohydrocarbyl, hydrocarbyloxy, halohydrocarbyloxy, hydrocarbylthio and halohydrocarbylthio radicals which are free of aliphatic unsaturation and contain from '1 to 12 carbon atoms and wherein two R's taken together stand for a radical selected from the class -O-hydrocarbylene-O- and O-halohydrocarbylene-O radicals which are free of aliphatic unsaturation and which contain from 2 to 10 carbon atoms; R" is selected from the class consisting of hydrocarbyl, halohydrocarbyl, hydr-ocarbyloxy and halohydrocarbyl'oxy which are free of aliphatic unsaturation and contain from 1 to 12 carbon atoms; Z is selected from the class consisting of hydrogen and hydrocarbyl radicals which are free of aliphatic unsaturation and which contain from 1 to 17 carbon atoms when n is 2 and from 1 to 10 carbon atoms when n is less than 2', Z' is selected from the class consisting of hydrogen and the methyl radical and is methyl only when Z is an alkyl radical of from 1 to 2 carbon atoms; and, when'n' is 2, Z and Z taken together With the carbon atom to which they are attached complete the cyclohexane ring; and R and R" are selected from the class consisting of alkyl, haloalkyl, aryl, haloaryl, alkoxy and haloalkoxy radicals of from 1 to 12 carbon atoms.

2. A lubricating composition comprising a major amount of a mineral lubricating oil and, based upon said oil, a minor amount by weight of a compound of the formula I C. L I

wherein n is a number of 0 to 2, each R is selected from the class consisting of hydrocarbyl, halohydrocarbyl, hydrocarbyloxy, halohydrocarby-loxy, hydrocarbylthio and halohydrocarbylthio radicals which are free of aliphatic unsaturation and contain from 1 to 12 carbon atoms and wherein two R's taken together stand for a radical selected from the class ,--O-hydrocarbylene-O and -O-halohydrocarbylene-O- radicals which are free of aliphatic unsaturation and which contain from 2 to 10 carbon atoms; Z is selected from the class consisting of hydrogen and hydrocarbyl radicals which are free of aliphatic unsaturation and which contain from 1 to 17 carbon atoms when n is 2 and from 1 to 10 carbon atoms when n is less than 2; Z' is selected from the class consisting of hydrogen and the methyl radical and is methyl only when Z 3. A lubricating composition comprising a major amount of a mineral lubricant :oil and, based upon said oil, a minor amount by weight of a compound of the formula wherein X is a haloalkyl radical of from 2 to 12 carbon atoms and alk denotes an alkyl radical of from 1 to 17 carbon atoms.

4. A lubricating composition comprising a major amount of a mineral lubricating oil and, based upon said oil, a minor amount by weight of, a compound of the formula wherein A is a hydrocarbylene radical which is free of aliphatic unsaturation and contains from 2 to carbon atoms, Z denotes a hydrocarbyl radical which is free of aliphatic unsaturation and contains from 1 to 17 carbon atoms, and T denotes an alkyl radical of from 1 to 12 carbon atoms.

5. A lubricating composition comprising a major proportion of a mineral lubricating oil and based upon said oil from 0.1 to 10% by weight :of 2-[2-(diethoxyphosphinyl)propyl]-1,3,2-dioxaphospholane.

6. A lubricating composition comprising a major proportion of a mineral lubricating oil and based upon said oil from 0.1% to 10% by weight of 1-[bis(2-chloropropoxy)phosphinyl]ethyl bis(2-chloropropyl) phosphite.

7. A lubricating composition comprising a major proportion of a mineral lubricating oil and .based upon said oil from 0.1% to 10% by weight of 1-[bis(2-chloropropoxy)phosphinyl]heptyl bis(2-chloropropy1) phosphite.

8. A composition of matter comprising a major proportion of a mineral lubricating oil and, based upon said oil, a minor amount of a compound having the formula II (haloar l-snrot lrrr (o T);

wherein the haloaryl radical has from 6 to 12 carbon atoms; Z is an alkyl radical of from 1 to 17 carbon atoms, and T is an alkyl radical of from 1 to 12 carbon atoms.

9. A lubricating composition of matter comprising a major proportion of a mineral lubricating oil and based upon said oil from 0.1 to 10% of l-(diethoxyphosphiny1)propyl S,S-bis(4-chlorophenyl) phosphorodithioite.

10. A lubricating composition which comprises a major amount of a mineral lubricating oil and, based upon said oil, a minor amount of a compound having the formula wherein T is an alkyl radical of from 1 to 12 carbon atoms.

11. A lubricating composition comprising a major proportion of a mineral lubricating oil and based upon said oil from 0.1% to 10% by weight of Z-[I-(diethoxyphosphinyl)cyclohexyloxy]-1,3,2-dioxaphospholane.

12. A lubricating composition comprising a major amount of a mineral lubricating oil and, based upon said oil, a minor amount by weight of a compound of the formula wherein T is an alkyl .radical of from 1 to 12 carbon atoms.

13. A lubricating composition comprising a major proportion of a mineral lubricating oil and based upon said oil from 0.1% to 10% by weight of 2-[l-(dihexyl-oxyphosphinyl)cyc1ohexyl]-4,5 benzo 1,3,2 dioxaphospholane.

14. A lubricating composition comprising a major amount of a mineral lubricating oil and, based upon said oil, a minor amount by weight of a compound of the formula wherein X is a haloalkyl radical of from 2 to 12 carbon atoms and alk denotes an alkyl radical of from 1 to 17 carbon atoms.

15. A lubricating composition comprising a major amount of a mineral lubricating oil and, based upon said oil, from 0.1% to 10% by weight of 1-[bis(2-chloropropoxy)phosphinyl]propy1 0,0-bis(2-chloropropyl) phosphorothioate.

16. A lubricating composition comprising a major amount of a mineral lubricating oil and, based upon said oil, from 0.1% to 10% by weight of 1-[bis(2-chloropropoxy)phosphinyl]heptyl 0,0-bis(2-chloropropyl) phosphorothioate.

17. A lubricating composition comprising a major amount of a mineral lubricating oil and, based upon said oil, a minor amount by weight of a compound of the formula wherein T denotes an alkyl radical having from 1 to 12 carbon atoms, and Z denotes an aryl radical having from 6 to 10 carbon atoms.

18. A lubricating composition comprising a major amount of a mineral lubricating oil and, based upon said oil, from 0.1% to 10% by weight of 0,0,0-tris[a-(dihexyloxyphosphinyl)benzyl] phosphorothioate.

19. A lubricating composition comprising a major proportion of a mineral lubricating oil and based upon said oil from 0.1 to 10% by weight of the bis(2-ch1oroethyl) phosphite of bis(2-chloroethyl) (l-hydroxyun decyl) phosphonate.

'35 36 v 20. A lubricating composition comprising a major .atoms, alk denotes an alkyl radical of from -1 to 17 carbon proportion of a mineral lubricating oil and, based upon atoms, and n has an average value of 1.

said oil, from 0.1% to 10% by weight of 1-[bis(2-chloro- 22. A lubricating composition comprising a major propoxy) phosphinyl1-2 ethylhexyl bis(2 -chloropr-opyl) amount of a mineral lubricating oil and, based upon said phosphate. 5 oil, from 0.1% to 10% by weight of a compound of the 21. A lubricating composition comprising a major formula 0 II I ll I ll CH3CHC1CH2OPOCHP OCHP-OCH:CHC1OH:4

A LI 1 1 CH3 OCHzCHClOHa I. CHa

amount of a mineral lubricating oil and, based upon said wherein n has an average value of 1. oil a minor amount by weight, of a compound of the f l References Cited by the Examiner i I" (I? (I? 15 UNITED STATES PATENTS (XO P-OCHP-OCH-POX 2,807,636 9/1957 Buls et al 26046'1.303

j: l- A) J I 2 DANIEL E. WYMAN, Primary Examiner.

wherein X is a haloalkyl radical of from 2 to 12 carbon JULIUS GREENWALD, Examiner. 

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR AMOUNT OF A MINERAL LUBRICATING OIL AND, BASED UPON SAID OIL A MINOR AMOUNT BY WEIGHT OF A COMPOUND OF THE FORMULA 